Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/66—Mercaptans
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
  • C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
  • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
  • H01L23/293—Organic, e.g. plastic
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
  • H01L2924/0001—Technical content checked by a classifier
  • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

• the present invention relates to an epoxy resin composition that is excellent in low-temperature rapid curing properties, has a low Tg (glass transition point) of the cured product, and does not change the Tg of the cured product almost even after a long time after curing.
• a resin composition comprising an epoxy resin, a thiol compound, and a curing accelerator is a resin composition excellent in low-temperature fast-curing property that can be cured in a short time even from 0 ° C. to ⁇ 20 ° C., and is used for sealing adhesives and electronic components. It is used for various applications such as agents.
• Patent Documents 1 and 2 include (1) an epoxy resin having two or more epoxy groups in the molecule, (2) a polythiol compound having two or more thiol groups in the molecule, And (3) a resin composition containing a solid dispersion type latent curing accelerator is disclosed.
• Patent Document 3 discloses an epoxy resin composition containing a bisphenol A type epoxy resin having a flexible skeleton and a polar bonding group and a polythiol having two or more thiol groups.
• JP-A-6-211969 Japanese Patent Laid-Open No. 6-21970 JP 2006-36935 A
• the adhesive for joining these parts needs to be flexible enough to follow the thermal deformation of the parts, and has a low Tg (glass transition point) after the adhesive is cured.
• the elastic modulus is required to be low.
• the epoxy resin compositions described in Patent Documents 1 and 2 described above have a problem that Tg cannot be sufficiently lowered although excellent low-temperature curability and storage stability can be obtained.
• the epoxy resin composition described in the above-mentioned patent document 3 can be cured at a low temperature and the cured product has a certain degree of flexibility and flexibility, it can absorb stress.
• the time passes the cured product is further cured and the flexibility and flexibility are gradually lost.
• the present invention has been made in view of the above-described problems, and is excellent in low-temperature rapid curability, has a low Tg (glass transition point) of the cured product, and is cured even after a long time after curing.
• An object of the present invention is to provide an epoxy resin composition in which the Tg of the resin hardly changes.
• the present inventors contain an epoxy resin that does not contain a benzene ring, a thiol compound having two or more thiol groups in the molecule, and a latent curing agent. It has been found that the resin composition to be cured is excellent in low-temperature rapid curability, the Tg of the cured product is low, and the Tg of the cured product hardly changes even after a long time after curing.
• the present invention is a resin composition containing (A) an epoxy resin not containing a benzene ring, (B) a thiol compound having two or more thiol groups in the molecule, and (C) a latent curing agent.
• the component (A) is preferably a compound represented by the following formula (1).
• the component (A) is preferably a compound represented by the following formula (2).
• the component (A) is preferably a compound represented by the following formula (3).
• the component (A) is preferably a compound represented by the following formula (4).
• the component (B) is preferably blended at a thiol equivalent ratio of 1.0 to 2.0 with respect to the epoxy equivalent of the component (A).
• the component (B) is tetraethylene glycol bis3-mercaptopropionate, trimethylolpropane tris3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and di Pentaerythritol is preferably at least one selected from tetrakis 3-mercaptopropionate.
• the resin composition of the present invention further includes at least one additive selected from the group consisting of a silica filler, a silane coupling agent, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, and a tampering agent. It is preferable to contain.
• this invention provides the electronic component sealed with the sealing agent containing either of the said resin compositions.
• the present invention also provides an adhesive containing any one of the above resin compositions.
• an epoxy resin composition that is excellent in low-temperature rapid curability, has a low Tg (glass transition point) of a cured product, and has a Tg that hardly changes even after a long time after curing. .
• a resin composition according to an embodiment of the present invention includes (A) an epoxy resin not containing a benzene ring, (B) a thiol compound having two or more thiol groups in the molecule, and (C) a latent curing agent. contains.
• the epoxy resin as the component (A) is preferably a compound represented by the following formula (1), for example.
• the compound represented by the above formula (1) is preferably, for example, a compound represented by the following formula (2) and / or formula (3).
• the compound represented by the said Formula (1) is a compound represented, for example by the following formula
• R 2 to R 5 are preferably methyl groups.
• the thiol compound as the component (B) may be any compound having two or more thiol groups per molecule. From the viewpoint of storage stability, those having as little basic impurity content as possible are preferred. Examples of such thiol compounds include trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris ( ⁇ -thiopropionate), pentaerythritol tetrakis.
• esterification reaction of a polyol such as ( ⁇ -thiopropionate), dipentaerythritol poly ( ⁇ -thiopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate and mercapto organic acid
• a polyol such as ( ⁇ -thiopropionate), dipentaerythritol poly ( ⁇ -thiopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate and mercapto organic acid
• examples include thiol compounds obtained.
• thiol compounds 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol
• Alkyl thiol compounds such as: terminal thiol group-containing polyethers; terminal thiol group-containing polythioethers; thiol compounds obtained by reaction of epoxy compounds with hydrogen sulfide; terminal thiol groups obtained by reaction of polythiol compounds with epoxy compounds Thiol compounds; and the like.
• a thiol compound having two or more thiol groups in a molecule that has been subjected to dealkalization treatment and has an alkali metal ion concentration of 50 ppm or less is preferable.
• the latent curing agent of the component (C) is a compound that is insoluble in an epoxy resin at room temperature, is a compound that is solubilized by heating and functions as a curing accelerator, and is an imidazole compound that is solid at room temperature or a solid dispersion type Amine adduct-based latent curing accelerators such as reaction products of amine compounds and epoxy compounds (amine-epoxy adduct systems), reaction products of amine compounds with isocyanate compounds or urea compounds (urea-type adduct systems), etc. Can be mentioned.
• Examples of the epoxy compound used as a raw material for producing the solid dispersion type amine adduct type latent curing accelerator (amine-epoxy adduct type) used in the present invention include, for example, bisphenol A, bisphenol F, catechol, resorcinol and the like.
• Polyglycidyl ethers obtained by reacting polyhydric alcohols such as monohydric phenols or glycerin or polyethylene glycol with epichlorohydrin; hydroxycarboxylic acids such as p-hydroxybenzoic acid and ⁇ -hydroxynaphthoic acid and epichloro Glycidyl ether ester obtained by reacting with hydrin; polyglycidyl ester obtained by reacting polycarboxylic acid such as phthalic acid and terephthalic acid with epichlorohydrin; 4,4'-diaminodiphenylmethane and m- Ami Glycidylamine compounds obtained by reacting phenol and epichlorohydrin; and polyfunctional epoxy compounds such as epoxidized phenol novolak resin, epoxidized cresol novolak resin, epoxidized polyolefin, butyl glycidyl ether, phenyl glycidyl ether Monofunctional epoxy compounds such as g
• the amine compound used as another raw material for producing the solid dispersion type amine adduct-based latent curing accelerator used in the present invention has at least one active hydrogen capable of addition reaction with an epoxy group in the molecule. What is necessary is just to have at least one functional group selected from a secondary amino group, secondary amino group and tertiary amino group in the molecule. Examples of such amine compounds are shown below, but are not limited thereto.
• aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-dicyclohexylmethane; 4,4'-diaminodiphenylmethane , Aromatic amine compounds such as 2-methylaniline; heterocyclic rings containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, piperazine Compound; and the like.
• a compound having a tertiary amino group in the molecule is a raw material that provides a latent curing accelerator having excellent curing acceleration ability.
• Examples of such a compound include dimethylaminopropyl.
• Amine compounds such as amine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, 2-methylimidazole, 2-ethylimidazole, 2-ethyl Primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as -4-methylimidazole and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol , 1-phenoxime 2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-di
• an active hydrogen compound having two or more active hydrogens examples include polyphenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, phenol novolac resin, polyhydric alcohols such as trimethylolpropane, polyhydric alcohols such as adipic acid and phthalic acid.
• active hydrogen compounds include carboxylic acids, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, and lactic acid.
• Examples of the isocyanate compound used as another production raw material of the solid dispersion type amine adduct-based latent curing accelerator used in the present invention include, for example, n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate and the like.
• Functional isocyanate compounds hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, Polyfunctional isocyanate compounds such as bicycloheptane triisocyanate; and further, these polyfunctional isocyanate compounds and active water Obtained by reaction of a compound, terminal isocyanate group-containing compound; and the like can also be used.
• terminal isocyanate group-containing compounds examples include addition compounds having terminal isocyanate groups obtained by reaction of toluylene diisocyanate and trimethylolpropane, and terminal isocyanate groups obtained by reaction of toluylene diisocyanate and pentaerythritol.
• the present invention is not limited thereto.
• examples of the urea compound include urea and thiourea, but are not limited thereto.
• the solid dispersion type latent curing accelerator used in the present invention includes, for example, (a) two components of an amine compound and an epoxy compound, (b) three components of the two components and an active hydrogen compound, or (c) an amine.
• a combination of two or three components of a compound and an isocyanate compound or / and a urea compound is mixed and reacted at a temperature of room temperature to 200 ° C. and then cooled and solidified and then ground, or methyl ethyl ketone, It can be easily obtained by reacting in a solvent such as dioxane or tetrahydrofuran, removing the solvent, and grinding the solid.
• urea-type adducts examples include “Fujicure FXE-1000” (trade name of Fuji Kasei Co., Ltd.) and “Fujicure FXR-1030”. (Fuji Kasei Co., Ltd.).
• the resin composition of the present invention can be prepared by mixing with a mixer such as a Henschel mixer.
• the resin composition of the present invention can be cured by heating at 50 to 120 ° C.
• the resin composition of the present invention is characterized by containing the components (A) to (C).
• the resin composition which is excellent in low temperature rapid curability and has low Tg (glass transition point) of hardened
• Tg glass transition point
• the component (B) is 1.0 to 2.0 (1.0 to 2.0) in terms of the thiol equivalent ratio with respect to the epoxy equivalent of the component (A). It is preferable that it is blended.
• “epoxy equivalent” is a numerical value obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups in one molecule.
• the “thiol equivalent” is a numerical value obtained by dividing the molecular weight of the thiol compound by the number of thiol groups in one molecule. That is, the component (B) has a thiol equivalent ratio of 1.0 to 2.0 with respect to the epoxy equivalent of the component (A) because the number of epoxy groups is 1 and the number of thiol groups is 1. It means 0.0-2.0.
• a resin composition in which Tg hardly changes can be obtained.
• the reason why such a resin composition is obtained is considered to be that the ratio of the thiol equivalent of the component (B) to the epoxy equivalent of the component (A) is set in an appropriate range. That is, when the thiol equivalent ratio of the component (B) to the epoxy equivalent of the component (A) is smaller than 1.0, a part of the epoxy group remains without reacting with the thiol group. It is considered that the curing of the cured product further proceeds due to the remaining epoxy group.
• the resin composition of the present invention is further selected from the group consisting of a silica filler, a silane coupling agent, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, and a tampering agent as necessary. It may contain at least one additive. Moreover, you may contain a viscosity modifier, a flame retardant, or a solvent.
• the resin composition of the present invention can be used as an adhesive or a raw material for bonding parts together.
• the resin composition of the present invention can be used as a sealant for electronic parts or a raw material thereof.
• the elastic modulus of the adhesive using the resin composition of the present invention is preferably 0.01 to 1.5 GPa, more preferably 0.4 to 0.8 GPa.
• the elastic modulus is smaller than 0.01 GPa, the cured portion of the adhesive becomes brittle.
• the elastic modulus is higher than 1.5 GPa, the cured product may crack in the shrinkage stress of the adhesive.
• the Tg of the adhesive using the resin composition of the present invention is preferably ⁇ 20 to ⁇ 55 ° C., more preferably ⁇ 30 to ⁇ 38 ° C. If Tg is greater than ⁇ 20 ° C., cracks may occur in the cured portion of the adhesive. In addition, cracks may occur in the adherend depending on the adhesive strength with the adherend. When Tg is smaller than ⁇ 55 ° C., the cured part becomes brittle.
• Resin compositions according to Examples 1 to 20 were prepared by mixing the components shown in Tables 1 and 2 below.
• the components shown in Table 3 below were mixed to prepare resin compositions according to Comparative Examples 1 to 4.
• the numbers indicating the blending ratio of the components (A) to (F) all indicate parts by weight.
• the elastic modulus was measured at ⁇ 40 ° C. using dynamic thermomechanical measurement (DMA) manufactured by Seiko Instruments Inc. according to Japanese Industrial Standard JIS C6481.
• DMA dynamic thermomechanical measurement
• Tg was measured using a dynamic thermomechanical measurement (DMA) manufactured by Seiko Instruments Inc. according to Japanese Industrial Standard JIS C 6481.
• DMA dynamic thermomechanical measurement
• the adhesive strength was measured using the following test method. (1) A sample is stencil printed on a glass epoxy substrate with a size of 2 mm ⁇ . (2) Place a 2 mm x 2 mm Si chip on the printed sample. This is cured for 60 minutes at 180 ° C. using a blow dryer. (3) The shear strength is measured with a desktop universal testing machine (1605HTP manufactured by Aiko Engineering Co., Ltd.).
• the resin composition of the present invention has a cured product having a modulus of elasticity at ⁇ 40 ° C. of 0.1 to 0.8 [Gpa] and a small modulus of elasticity.
• the resin composition according to Comparative Example has an elastic modulus at ⁇ 40 ° C. of 4.0 [GPa], and a cured product having a low elastic modulus can be obtained. There wasn't.
• the resin composition of the present invention had a Tg of ⁇ 50 ° C. to ⁇ 30 ° C. and a low Tg of the cured product.
• the resin composition according to the comparative example had a Tg of 40 ° C., and a cured product having a low Tg was not obtained.
• the resin composition of the present invention showed almost no change in the elastic modulus and Tg of the cured product even after being left at 120 ° C. for 48 hours after curing. From this, the resin composition of the present invention was able to demonstrate that Tg hardly changed even after a long time passed after curing.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Physics & Mathematics (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• General Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Computer Hardware Design (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Power Engineering (AREA)
• Epoxy Resins (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=46457373

Family Applications (1)

Country Status (4)

Cited By (18)

Families Citing this family (9)

Citations (5)

Family Cites Families (5)

• 2011
  • 2011-09-14 KR KR1020137020502A patent/KR101819785B1/ko active IP Right Grant
  • 2011-09-14 CN CN201180064158XA patent/CN103282401A/zh active Pending
  • 2011-09-14 WO PCT/JP2011/070917 patent/WO2012093510A1/ja active Application Filing
  • 2011-09-23 TW TW100134291A patent/TWI629291B/zh active

Patent Citations (5)

Also Published As

Similar Documents

Legal Events